Maltol-2-methyl pentenoates and organoleptic uses thereof

ABSTRACT

Described are maltol-2-methyl pentenoates having the structure: ##STR1## wherein R is a secondary pentenyl moiety having one of the structures: ##STR2## AS WELL AS METHODS FOR PREPARING FOODSTUFFS, FLAVORING COMPOSITIONS FOR FOODSTUFFS, CHEWING GUM COMPOSITIONS, FLAVORING COMPOSITIONS FOR CHEWING GUM, MEDICINAL PRODUCT COMPOSITIONS AND INGREDIENTS FOR MEDICINAL PRODUCT COMPOSITIONS BY INCLUDING THEREIN SAID MALTOL-2-METHYL PENTENOATES WHICH AUGMENT OR ENHANCE THE FLAVOR OR AROMA OF SAID COMPOSITIONS.

BACKGROUND OF THE INVENTION

The present invention relates to maltol-2-methyl pentenoates and novelcompositions using such maltol-2-methyl pentenoates to augment orenhance the flavor or aroma of foodstuffs, chewing gums and medicinalproducts.

There has been considerable work performed relating to substances whichcan be used to impart (or enhance) flavors to (or in) various consumablematerials, e.g., foodstuffs, medicinal products and chewing gums. Thesesubstances are used to diminish the use of natural materials, some ofwhich may be in short supply and to provide more uniform properties inthe finished product. Sweet, strawberry-like, fruity, red berry, green,winey and cognac-like aromas as well as sweet, fruity, strawberry, berryand winey tastes are particularly desirable for many uses in foodstuffflavors, medicinal product flavors and chewing gum flavors; particularlystrawberry flavors, raspberry flavors, wine flavors and cognac flavors.

U.S. Pat. No. 4,000,327 issued on Dec. 28, 1976 describes the use inberry fruit flavors of a synthetically produced 6-carbon carboxylic acidester-containing composition comprising as its major constituent acis-ester of 2-methyl-3-pentenoic acid having the structure: ##STR3##wherein R is one of ethyl, isobutyl or n-hexyl.

U.S. Pat. No. 3,499,769 issued on Mar. 10, 1970 discloses processes forimparting a fresh fruity flavor (particularly strawberry flavor) tofoods by adding a small amount of 2-methyl-2-pentenoic acid to thefoodstuff. In U.S. Pat. No. 3,499,769 it is emphasized that the basicnuance imparted by 2-methyl-2-pentenoic acid is a "berry" flavor.

Maltol, having the structure: ##STR4## is well known for its use instrawberry flavors. It is described by Arctander, "Perfume and FlavorChemicals (Aroma Chemicals)" at number 1831 to have a warm fruity,caramellic-sweet odor with emphasis on the caramellic note in the drystate. Solutions of maltol are indicated by Arctander to show apronounced fruity, jam-like odor of pineapple, strawberry types.Arctander further states that maltol is "intensely sweet, fruity,jam-like, . . . having a pineapple, strawberry type flavor withcaramellic undertone". It is stated that the caramellic effect ispredominant at high (20-100 ppm) concentrations while the fruity effectis most attractive at much lower concentrations. It is stated byArctander that the main use of maltol is in flavor compositions not onlyas a fruity component in pineapple and strawberry, but in general, as asweetener.

In addition, maltyl esters of alkanoic acids are known as flavorants.Thus, on the GRAS list (generally recognized as safe by the FlavorExtracts Manufacturers' Association) maltyl isobutyrate (number 3462,Food Technology, August 1975, page 72) is set forth. On that same page,2-methyl-3-pentenoic acid is set forth as number 3464.

U.S. Pat. No. 2,766,148 issued on Oct. 9, 1956 sets forth theimprovement in the flavor and aroma of tobacco by addition thereto offrom 0.01 up to 1.0% of esters including maltol-3-methyl-valerate.

None of the prior art however sets forth compounds having structuresrelated to the maltol-2-methyl pentenoates of the present invention.Furthermore, the properties of the maltol-2-methyl pentenoates of thepresent invention, from an organoleptic standpoint, are considered to beunobvious, unexpected and advantageous with respect to the organolepticproperties of the esters of the prior art set forth above.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents the GLC profile for the reaction product of Example I,which is maltyl-2-methyl-3-pentenoate having a high proportion (greaterthan 50%) of maltyl-2-methyl-cis-3-pentenoate.

FIG. 2 represents the NMR spectrum for maltyl-2-methyl-3-pentenoateproduced according to Example I.

FIG. 3 represents the Infrared spectrum for the reaction product ofExample I, which is maltyl-2-methyl-3-pentenoate.

FIG. 4 represents the GLC profile for the reaction product of ExampleII, which is maltyl-2-methyl-2-pentenoate.

FIG. 5 represents the NMR spectrum for the reaction product of ExampleII, which is maltyl-2-methyl-2-pentenoate.

FIG. 6 represents the Infrared spectrum for the reaction product ofExample II, which is maltyl-2-methyl-2-pentenoate.

FIG. 7 represents the GLC profile for the reaction product of ExampleIII, which is maltyl tiglate.

FIG. 8 represents the NMR spectrum for the reaction product of ExampleIII, which is maltyl tiglate.

THE INVENTION

This invention relates to maltol-2-methyl pentenoates having the genericstructure: ##STR5## wherein R represents a secondary pentyl moietyhaving one of the structures: ##STR6##

It has now been discovered that solid and liquid foodstuffs, chewinggums, medicinal products and flavoring compositions therefor havingsweet, strawberry-like, fruity, red berry, green, winey and cognac-likearomas and sweet, fruity, strawberry, berry and winey tastes may beprovided by the utilization of maltol-2-methyl pentenoates.

The maltol-2-methyl pentenoates of our invention may be prepared byreacting maltol with the appropriate acyl halide which, in turn, may beformed from the corresponding alkenoic acid with thionyl chloride(SOCl₂). This reaction sequence is generically set forth as follows:##STR7## wherein R is one of the moieties: ##STR8## In place of thionylchloride, thionyl bromide may be used and the corresponding acyl bromidemay be reacted with maltol.

Although the maltol-2-methyl pentenoates of our invention are novel, theprocesses for preparing same as set forth above and conditions for suchprocesses are set forth in "Reagents for Organic Synthesis", Fieser &Fieser, John Wiley & Sons, Inc. publishing company, 1967 at pages 1158and 1159 and "Organic Syntheses Collective Volume III", E. C. Horning,John Wiley & Sons, Inc. publishing company, 1955 at pages 714 and 715.

Examples of the maltol-2-methyl pentenoates of our invention and theirorganoleptic properties are as follows:

    ______________________________________                                        Name and Structure   Organoleptic Properties                                  ______________________________________                                         ##STR9##            A fruity, berry, yeasty, winey, strawberry, maltol-li                         ke and cognac aroma with a fruity, berry, yeasty,                             winey, strawberry-like and allium taste at 10 ppm.       and                                                                            ##STR10##                                                                    cis and trans isomers)                                                         ##STR11##           A sweet, fruity, straw- berry-like and red berry                              aroma characteristic with sweet, fruity                                       and strawberry flavor char- acteristics and green                             nuances at 5 ppm.                                        and                                                                            ##STR12##                                                                    cis and trans isomers)                                                        ______________________________________                                    

Accordingly, the maltol-2-methyl pentenoates of our inventioncontemplate mixtures of cis and trans isomers and the individual cis andtrans isomers themselves. Thus, the specific cis and transisomerstructures of our invention are as follows: ##STR13##

When the maltol-2-methyl pentenoates of our invention are used as a foodflavor adjuvant, or a chewing gum flavor adjuvant or a medicinal productflavor adjuvant, the nature of the co-ingredients included with the saidmaltol-2-methyl pentenoates in formulating the product composition willalso serve to alter the organoleptic characteristics of the ultimatefoodstuff or chewing gum or medicinal product treated therewith.

As used herein, in regard to flavors the term "alter" in its variousforms means "supplying or imparting flavor character or note tootherwise bland, relatively tasteless substances or augmenting theexisting flavor characteristic where a natural flavor is deficient insome regard or supplementing the existing flavor impression to modifyits quality, character or taste."

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks andthe like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible materials which have medicinal value suchas cough syrups, cough drops, laxatives, aspirin, chewable medicinaltablets containing antibiotics and sore throat lozenges.

The term "chewing gum" is herein intended to be definitive of acomposition which comprises a substantially water-insoluble, chewable,plastic gum base such as chicle, or substitutes therefor, includingjelutong, guttakay rubber or certain comestible natural or syntheticresins or waxes. Incorporated with the gum base, and in admixturetherewith, may be plasticizers or softening agents, e.g., glycerine; anda flavoring composition which incorporates the maltol-2-methylpentenoates of our invention, and in addition sweetening agents whichmay be sugars including sucrose or dextrose and/or artificial sweetenerssuch as cyclamates or saccharin. Other optional ingredients may also bepresent.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use being extensivelydescribed in the relevant literature. Apart from the requirement thatany such material be "ingestibly" acceptable and thus non-toxic orotherwise non-deleterious, nothing particularly critical resides inselection thereof. Accordingly, such materials which may in general becharacterized as flavoring adjuvants or vehicles comprise broadlystabilizers, thickeners, surface active agents, conditioners, otherflavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2 and 3tertiary-butyl-4-hydroxyanisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectins and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g, sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, turmeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, beta, beta-dimethylacrolein, n-hexanal, 2-hexenal, cis-3-hexenal, 2-heptanal,4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,2-methyl-3-butanone, 2-pentanone, 2-pentenal and propanal; alcohols,such as 1-butanal, benzyl alcohol, 1-borneol, trans-2-buten-1-ol,ethanol, geraniol, 1-hexanal, 2-heptanol, trans-2-hexenol-1,cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentenol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate; esters, suchas butyl acetate, ethyl acetate, ethyl acetoacetate, ethyl benzoate,ethyl butyrate, ethyl caproate, ethyl cinnamate, ethyl crotonate, ethylformate, ethyl isobutyrate, ethyl isovalerate, ethylalpha-methylbutyrate, ethyl propionate, ethyl salicylate,trans-2-hexenyl acetate, hexyl acetate, 2-hexenyl butyrate, hexylbutyrate, isoamyl acetate, isopropyl butyrate, methyl acetate, methylbutyrate, methyl capronate, methyl isobutyrate, alpha-methylbutyrate,propyl acetate, amyl acetate, amyl butyrate, benzyl salicylate, dimethylanthranilate, ethyl methylphenylglycidate, ethyl succinate, isobutylcinnamate and terpenyl acetate; essential oils, such as jasmineabsolute, rose absolute, orris absolute, lemon essential oil, Bulgarianrose, yara yara, natural raspberry oil and vanilla; lactones; sulfides,e.g., methyl sulfide and other materials such as maltol, acetoin andacetals (e.g., 1,1-diethoxyethane, 1,1-dimethoxyethane anddimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, medicinal product or chewing gum, whether simulated ornatural, and should, in any event, be capable of providing anenvironment in which the maltol-2-methyl pentenoates of our inventioncan be dispersed or admixed to provide a homogeneous medium. Inaddition, selection of one or more flavoring adjuvants, as well as thequantities thereof, will depend upon the precise organoleptic characterdesired in the finished product. Thus, in the case of flavoringcompositions, ingredient selection will vary in accordance with thefoodstuff or chewing gum or medicinal product to which the flavor andaroma are to be imparted. In contradistinction, in the preparation ofsolid products, e.g., simulated foodstuffs, ingredients capable ofproviding normally solid compositions should be selected such as variouscellulose derivatives.

As will be appreciated by those skilled in the art, the amount ofmaltol-2-methyl pentenoates employed in a particular instance can varyover a relatively wide range whereby to its desired organoleptic effectshaving reference to the nature of the product are achieved. All partsand percentages given herein are by weight unless otherwise specified.Thus, correspondingly greater amounts would be necessary in thoseinstances wherein the ultimate food composition or chewing gumcomposition or medicinal product composition to be flavored isrelatively bland to the taste, whereas relatively minor quantities maysuffice for purposes of enhancing the composition merely deficient innatural flavor or aroma. Thus, the primary requirement is that theamount selected to be effective, i.e., sufficient to alter theorganoleptic characteristics of the parent composition, whetherfoodstuff per se, chewing gum per se, medicinal product per se orflavoring composition. Thus, the use of insufficient quantities ofmaltol-2-methyl pentenoates of our invention will, of course,substantially vitiate any possibility of obtaining the desired resultswhile excess quantities prove needlessly costly and in extreme cases,may disrupt the flavor-aroma balance, thus proving self-defeating.Accordingly, the terminology, "effective amount" and "sufficient amount"is to be accorded a significance in the context of the present inventionconsistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, ultimate chewinggum compositions and ultimate medicinal product compositions, it isfound that quantities of maltol-2-methyl pentenoates ranging from asmall but effective amount, e.g., 0.01 parts per million up to about 50parts per million by weight based on total composition are suitable.Concentrations in excess of the maximum quantity stated are not normallyrecommended since they fail to prove commensurate enhancement oforganoleptic properties. In those instances wherein the maltol-2-methylpentenoates are added to the foodstuff or chewing gum or medicinalproduct, as the case may be, as an integral component of a flavoringcomposition, it is, of course, essential that the total quantity offlavoring composition employed be sufficient to yield an effectivemaltol-2-methyl pentenoate concentration in the foodstuff product,medicinal product or chewing gum.

Medicinal product, chewing gum and food flavoring compositions preparedin accordance with the present invention preferably contain themaltol-2-methyl pentenoates in concentrations ranging from about 0.15%up to about 10% by weight based on the total weight of said flavoringcomposition.

The compositions described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitjuices and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively, theflavoring compositions in the form of particulate solids can beconveniently prepared by mixing the maltol-2-methyl pentenoates with,for example, gum arabic, gum tragacanth, carrageenan and the like, andthereafter spray-drying the resultant mixture whereby to obtain theparticular solid product. Pre-prepared flavor mixes in powder form,e.g., a vanilla powder mix or a walnut flavored powder mix are obtainedby mixing the dried solid components, e.g., starch, sugar and the likeand maltol-2-methyl pentenoates of our invention in a dry blender untilthe requisite degree of uniformity is achieved.

It is presently preferred to combine with the maltol-2-methylpentenoates of our invention the following adjuvants:

Geraniol

Ethyl methyl phenyl glycidate

Vanillin

Ethyl pelargonate

Isoamyl acetate

Ethyl butyrate

Maltol

Naphthyl ethyl ether

Ethyl acetate

Isoamyl butyrate

2-Methyl-2-pentenoic acid

Elemecine (4-allyl-1,2,6-trimethoxy benzene)

Isoelemecine (4-propenyl-1,2,6-trimethoxy benzene)

High cis 2-methyl-3-pentenoic acid isomer mixtures produced according toU.S. Pat. No. 3,984,579

Ethyl-2-methyl-cis-3-pentenoic acid ester produced according to U.S.Pat. No. 4,000,327

Isobutyl-2-methyl-cis-3-pentenoic acid ester produced according to U.S.Pat. No. 4,000,327

n-Hexyl-2-methyl-3-pentenoic acid ester produced according to U.S. Pat.No. 4,000,327

Maltol isobutyrate

The following Examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. The followingExamples are given to illustrate methods for preparing maltol-2-methylpentenoates useful in the practice of our invention. It will beunderstood that these Examples are illustrative, and the invention isnot to be considered as restricted thereto except as indicated in theappended claims.

EXAMPLE I PREPARATION OF MALTYL-2-METHYL-CIS-3-PENTENOATE MIXTURE

Reaction ##STR14##

Procedure

Into a 250 ml two necked reaction flask equipped with mechanicalstirrer, Fredrich's condenser and gas trap, 12 g of a mixture containinga high proportion of 2-methyl-cis-3-pentenoic acid prepared according toExample VII at column 18 of U.S. Pat. No. 3,984,579 issued on Oct. 5,1976, in 50 ml benzene is added. Fredrich's condenser side arm isequipped in such a way as to vent the gases released through a trap intoa beaker containing commercial preparation of sodium hypochlorite(Clorox®). With vigorous stirring, 11.9 grams of freshly distilledthionyl chloride are added to the reaction mixture. The reaction mixtureis then stirred and heated until no more hydrogen chloride or sulfurdioxide gas is released (over a period of 45 minutes). The reaction massis then allowed to cool and 12.6 grams of maltol and 50 ml of benzeneare added thereto. The mixture is again heated until no more gas evolves(period of time: 45 minutes). The benzene solvent is then removed on arotary evaporator. The resulting reaction product,maltyl-2-methyl-3-pentenoate containing a high proportion (80%) ofmaltyl-2-methyl-cis-3-pentenoate and 20%maltyl-2-methyl-trans-3-pentenoate is trapped on a preparative GLCcolumn. Conditions: 12' × 3/8" 20% SE-52 column programmed at 100-190°C. at 8° C. per minute.

A total of 0.55 grams of maltyl-2-methyl-3-pentenoate is collectedhaving a purity of greater than 99%.

The GLC profile for the reaction product is set forth in FIG. 1. The NMRspectrum is set forth in FIG. 2. The Infrared spectrum formaltyl-2-methyl-3-pentenoate is set forth in FIG. 3.

EXAMPLE II PREPARATION OF MALTYL-2-METHYL-2-PENTENOATE

Reaction ##STR15##

Procedure

119 Grams of thionyl chloride is distilled immediately before using(75-76° C. at 760 mm pressure). While the thionyl chloride is beingdistilled, 114 grams of 2-methyl-2-pentenoic acid (mixture of cis andtrans isomers prepared according to the procedure of U.S. Pat. No.3,499,769 issued on Mar. 10, 1970) is melted using warm water. Themelted 2-methyl-2-pentenoic acid and distilled thionyl chloride are thenslowly added to a 1 liter three necked round bottomed flask equippedwith a mechanical stirrer and a Fredrich's condenser, the side arm ofwhich is equipped with a trap to vent the gas released into a beaker of5% sodium carbonate. The mixture is stirred and heated for a period of 1hour. The mixture is then cooled and maltol (126 grams) dissolved in 200cc of benzene is added. The reaction mass is then heated to reflux andstirred for a period of two hours. After cooling, the reaction mass isfiltered to recover a maltol precipitate. The supernatant liquid is thenadded to a separatory funnel and extracted with three volumes of 5%sodium carbonate. The supernatant liquid is then washed with water. Thebenzene is then removed using a rotary evaporator and the resultingproduct is recrystallized from ethyl acetate. The sodium carbonate layeris acidified with 2 molar aqueous hydrochloric acid and extracted with10% volumes of diethyl ether; then washed with water and dried overanhydrous sodium sulfate; then concentrated to 3.60 grams of residue.This residue is determined to be 2-methyl-2-pentenoic acid.

The recrystallization product from ethyl acetate weighs 30.62 grams andis identified as maltyl-2-methyl-2-pentenoate having a purity of 99.46%(yield: 13.8%).

The GLC profile for the reaction product containingmaltyl-2-methyl-2-pentenoate is set forth in FIG. 4. The NMR spectrumfor maltyl-2-methyl-2-pentenoate is set forth in FIG. 5. The Infraredspectrum for maltyl-2-methyl-2-pentenoate is set forth in FIG. 6.

EXAMPLE III PREPARATION OF MALTYL TIGLATE

Reaction ##STR16##

Procedure

10 Grams of tiglic acid dissolved in 50 ml anhydrous benzene are placedin a 250 ml two necked reaction flask equipped with mechanical stirrerand Fredrich's condenser, whose side arm is equipped in such a way as tovent the gases released during the reaction through a trap and into abeaker containing a solution of sodium hypochlorite (Clorox®). 11.9Grams of thionyl chloride (freshly distilled) are added to the reactionmass. The mixture is then stirred and heated until no additionalhydrogen chloride or sulfur dioxide is released (period: 60 minutes).The reaction mass is then allowed to cool and 12.6 grams of maltol and50 cc of benzene are added. The reaction mass is then heated to refluxuntil no more sulfur dioxide or hydrogen chloride gas is released(period: 1 hour). The benzene is removed on a rotary evaporator.

The reaction mass solidifies upon refrigeration and is then dissolved inethyl acetate and placed in a freezer. The resultant crystals arefiltered and washed with ethyl acetate. The material is then purified byrecrystallization from ethyl acetate and a 96.9% pure material isobtained. This material is maltyl tiglate.

The GLC profile for the reaction product is set forth in FIG. 7. The NMRspectrum for maltyl tiglate is set forth in FIG. 8.

EXAMPLE IV

The following basic strawberry flavor formulation is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Parahydroxy benzyl acetone                                                                           2                                                      Vanillin               15                                                     Maltol                 20                                                     Ethyl methyl phenyl glycidate                                                                        15                                                     Benzyl acetate         20                                                     Ethyl butyrate         10                                                     Methyl cinnamate       5                                                      Methyl anthranilate    5                                                      Alpha ionone           1                                                      Gamma undecalactone    2                                                      Diacetyl               2                                                      Anethole               1                                                      Cis-3-hexenol          17                                                     Ethyl alcohol (95% aqueous food                                               grade)                 385                                                    Propylene glycol       500                                                    ______________________________________                                    

At the rate of 6%, to half of the above-mentioned formulation,maltyl-2-methyl-3-pentenoate prepared according to Example I (C.A.S.name: 3-hydroxy-2-methyl-4H-pyran-4-one) is added. The basic strawberryformulation with the maltyl-2-methyl-3-pentenoate is compared to thebasic strawberry formulation without said maltyl-2-methyl-3-pentenoate.Both flavors are compared at the rate of 50 ppm in water and evaluatedby a bench panel composed of five individuals. The flavor containing themaltyl-2-methyl-3-pentenoate is found to have a sweet, fresh, morestrawberry-like aroma and taste. Therefore, it is preferred unanimouslyby the members of the bench panel as being more pleasant, morecharacteristic and as the better strawberry flavor.

EXAMPLE V PREPARATION OF MALTYL-2-METHYL-CIS-3-PENTENOATE

Reaction: ##STR17##

Thionyl chloride is immediately distilled before use (76° at 760 mmpressure) and added to 2-methyl-cis-3-pentenoic acid prepared accordingto Example XIV at column 30 of U.S. Pat. No. 3,984,579 issued on Oct. 5,1976. A 1 liter three necked round bottomed flask equipped with aFredrich's condenser, mechanical stirrer and heating mantle is then usedfor the reaction. The mixture of 2-methyl-cis-3-pentenoic acid andthionyl chloride is stirred and heated for a period of 1.5 hours (untilno more sulfur dioxide or hydrogen chloride gas is emitted). A trap isthen connected to the side arm of the Fredrich's condenser and ventedinto a beaker containing a 5% solution of sodium bicarbonate to trap theevolved hydrogen chloride and sulfur dioxide. The mixture is thenallowed to cool to room temperature and 126 grams of maltol in 200 cc ofbenzene is added. The reaction mass is then heated to reflux for aperiod of one hour and then cooled. The unreacted 2-methyl-cis-3-pentenoic acid is extracted with 10 equal volumes of 5% sodiumcarbonate. The resulting reaction product is then washed with water. Theresulting mixture is then filtered and the solid is determined to beunreacted maltol (27.44 grams or 44.76%). The benzene is then removedfrom the supernatant liquid by means of a rotary evaporator, gaschromatography indicating that there remains some2-methyl-cis-3-pentenoic acid and benzene. The resulting product waspurified by means of vacuum distillation whereby the benzene and2-methyl-cis-3-pentenoic acid are removed. The impurities are distilledoff at 4 mm Hg pressure at 70°-80° C. The maltyl-2-cis-3-pentenoateresulting is greater than 99% pure. Yield=114.01 grams or 51.36%.

The sodium carbonate layer is acidified with 2 molar hydrochloric acidand extracted with three 10% volumes of diethyl ether and concentratedto yield 18.9 grams of 34.08% residual 2-methyl-3-pentenoic acid.

GLC, NMR, IR and Mass Spectral data indicate that the material ismaltyl-2-methyl-cis-3-pentenoate.

EXAMPLE VI

The following concentrate is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Geraniol              1.0                                                     Ethyl methyl phenyl glycidate                                                                       3.0                                                     Maltyl-2-methyl-2-pentenoate                                                  prepared according to                                                         Example II            5.0                                                     Vanillin              6.0                                                     Ethyl pelargonate     13.0                                                    Isoamyl acetate       14.0                                                    Ethyl butyrate        58.0                                                    ______________________________________                                    

The resulting concentrate is dissolved in four volumes of propyleneglycol and the mixture is added to a hard candy melt at the rate of 1.5ounces of the concentrate in 100 pounds of melt. After the finishedcandy has been produced, it is found to have an excellent strawberryflavor. When the candy is compared with candy made under the sameconditions but either (i) without the maltyl-2-methyl-2-pentenoate or(ii) with maltyl tiglate prepared according to Example III, it is foundto have an inferior strawberry flavor.

EXAMPLE VII

The following concentrate is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Geraniol               1.0                                                    Ethyl methyl phenyl glycidate                                                                        3.0                                                    Maltyl-2-methyl-cis-3-pentenoate                                               prepared according to the                                                     process of Example V  5.0                                                    Vanillin               6.0                                                    Ethyl pelargonate      13.0                                                   Isoamyl acetate        14.0                                                   Ethyl butyrate         58.0                                                   ______________________________________                                    

The resulting concentrate is dissolved in four volumes of propyleneglycol and the mixture is added to a hard candy melt at the rate of 1.5ounces of the concentrate in 100 pounds of melt. After the finishedcandy has been produced, it is found to have an excellent strawberryflavor. When the candy is compared with candy made under the sameconditions but either (i) without the maltyl-2-methyl-cis-3-pentenoateor (ii) with maltyl tiglate prepared according to Example III, it isfound to have an inferior strawberry flavor.

EXAMPLE VIII PART A: PREPARATION OF FLAVOR CAPSULES

Five hundred grams of water are heated to boil and 500 grams of dextrin(National Starch and Chemical Corporation, 78-1523) is added with rapidand efficient mixing, using a closed turbine, high shear mixer(Barrington CONVERTI JET Model CJ-5B). Mixing is continued until ahomogeneous solution is obtained.

PART B: PREPARATION OF FLAVOR CAPSULE COMPOSITION

81 Grams of maltyl-2-methyl-cis-3-pentenoate prepared according toExample I is emulsified in 300 grams of the shell composition solution(A) by means of a homogenizing mixer (Barrington CONVERTI JET ModelCJ-5B operated as a closed turbine unit). At the start of the operationthe temperature of the matrix composition solution is 20° C. and of themaltyl-2-methyl-cis-3-pentenoate 15° C. The mixing vessel is cooledduring the operation of the mixer in order to prevent a rise in thetemperature and to keep the temperature below 25° C.

PART C: CAPSULE FORMATION AND DEHYDRATION

One thousand grams of polyethylene glycol having an average molecularweight of 400 (Union Carbide Corporation, Carbowax 400) and at atemperature of about 25° C. is placed in a vessel equipped with ahomogenizing mixer (Barrington CONVERTI JET Model CJ-5B operated as anopen turbine unit). One hundred grams of themaltyl-2-methyl-cis-3-pentenoate produced according to Example I isintroduced into the polyethylene glycol in a thin stream with steadymedium speed operation of the mixer (about 1,500 rpm shaft speed). Bythe action of the mixer, the maltyl-2-methyl-cis-3-pentenoate is brokenup into coarse liquid particles, which in contact with the polyethyleneglycol, are rapidly converted into gel particles and finally intovirtually anhydrous capsule granules.

The capsule granules are separated from the excess polyethylene glycolby means of a basket centrifuge and added to chewing gum, toothpaste,chewable vitamin tablets and chewing tobacco as set forth infra.

EXAMPLE IX

The following mixture is prepared:

    ______________________________________                                        Ingredient             Parts by Weight                                        ______________________________________                                        Liquid Flavor Composition                                                     of Example IV          48.4                                                   Cab-O-Sil M-5           3.2                                                    (Brand of Silica produced by                                                  the Cabot Corporation of                                                      125 High Street, Boston, Mass.                                                02110; Physical Properties:                                                   Surface Area: 200m.sup.2 /gm                                                  Nominal Particle Size: 0.012                                                 microns                                                                        Density: 2.3 lbs./cu.ft.)                                                    ______________________________________                                    

The Cab-O-Sil is dispersed in the liquid flavor composition of ExampleIV with vigorous stirring, thereby resulting in a viscous liquid. 48.4Parts by weight of the encapsulated flavor composition of Example VIIIis then blended into said viscous liquid, with stirring at 25° C. for aperiod of 30 minutes, resulting in a thixotropic sustained releaseflavor paste.

EXAMPLE X CHEWING GUM

100 Parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example IX. 300 Parts by weight ofsucrose and 100 parts by weight of corn syrup are added. Mixing iseffected in a ribbon blender with jacketed side walls of the typemanufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant long lastingstrawberry flavor.

EXAMPLE XI TOOTHPASTE FORMULATION

The following separate groups of ingredients are prepared:

    ______________________________________                                        Parts by Weight  Ingredient                                                   ______________________________________                                        Group "A"                                                                     30.200           Glycerin                                                     15.325           Distilled Water                                               .100            Sodium Benzoate                                               .125            Saccharin Sodium                                              .400            Stannous Fluoride                                            Group "B"                                                                     12.500           Calcium Carbonate                                            37.200           Dicalcium Phosphate                                                            (Dihydrate)                                                 Group "C"                                                                     2.000            Sodium N-Lauroyl                                                               Sarcosinate (foaming                                                         agent)                                                       Group "D"                                                                     1.200            Flavor Material of                                                             Example IX                                                  100.00 (Total)                                                                ______________________________________                                    

PROCEDURE:

1. The ingredients in Group "A" are stirred and heated in a steamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogenous gel.

3. The powders of Group "B" are added to the gel, while mixing until ahomogeneous paste is formed.

4. With stirring, the flavor of "D" is added and lastly the sodiumn-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour. The completedpaste is then transferred to a three roller mill and then homogenized,and finally tubed.

The resulting toothpaste when used in a normal toothbrushing procedureyields a pleasant strawberry flavor, of constant strong intensitythroughout said procedure (1-1.5 minutes).

EXAMPLE XII CHEWABLE VITAMIN TABLETS

The flavor material produced according to the process of Example IX isadded to a Chewable Vitamin Tablet Formulation at a rate of 9 gm/gmwhich Chewable Vitamin Tablet Formulation is prepared as follows:

In a Hobart Mixer, the following materials are blended to homogeneity:

    ______________________________________                                                             Gms/1000 tablets                                         ______________________________________                                        Vitamin C (ascorbic acid)                                                     as ascorbic acid-sodium                                                       ascorbate mixture 1:1  70.0                                                   Vitamin B.sub.1 (thiamine mononitrate)                                        as Rocoat thiamine mononitrate                                                33 1/3% (Hoffman La Roche)                                                                           4.0                                                    Vitamin B.sub.2 (riboflavin)                                                  as Rocoat riboflavin 33 1/3%                                                                         5.0                                                    Vitamin B.sub.6 (pyridoxine hydrochloride)                                    as Rocoat pyridoxine hydrochloride                                            33 1/3%                4.0                                                    Niacinamide                                                                   as Rocoat niacinamide 33 1/3%                                                                        33.0                                                   Calcium pantothenate   11.5                                                   Vitamin B.sub.12 (cyanocobalamin)                                             as Merk 0.1% in gelatin                                                                              3.5                                                    Vitamin E (dl-alpha tocopheryl acetate)                                       as dry Vitamin E acetate 33 1/3% Roche                                                               6.6                                                    d-Biotin               0.044                                                  Certified lake color   5.0                                                    Flavor of Example IX   5.0                                                    Sweetener - sodium saccharin                                                                         1.0                                                    Magnesium stearate lubricant                                                                         10.0                                                   Mannitol q.s. to make  500.0                                                  ______________________________________                                    

Preliminary tablets are prepared by slugging with flat-faced punches andgrinding the slugs to 14 mesh. 13.5 Grams dry Vitamin A Acetate and 0.6grams Vitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 g each.

Chewing of the resultant tablets yields a pleasant, long-lasting,consistently strong strawberry flavor for a period of 12 minutes.

EXAMPLE XIII CHEWING TOBACCO

Onto 100 pounds of tobacco for chewing (85 percent Wisconsin leaf and 15percent Pennsylvania leaf) the following casing is spread at a rate of30 percent:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Corn Syrup             60                                                     Licorice               10                                                     Glycerine              20                                                     Fig Juice              4.6                                                    Prune Juice            5                                                      Flavor Material of Example IX                                                                        0.4                                                    ______________________________________                                    

The resultant product is redried to a moisture content of 20 percent. Onchewing, this tobacco has an excellent substantially consistent,long-lasting strawberry (20 minutes) nuance in conjunction with the mainfruity tobacco note.

What is claimed is:
 1. A maltyl-2-methyl-pentenoate having thestructure: ##STR18## wherein R is a moiety selected from the groupconsisting of: ##STR19##
 2. The maltyl-2-methyl-pentenoate of claim 1wherein R has the structure: ##STR20##
 3. The maltyl-2-methyl-pentenoateof claim 1 wherein R has the structure: ##STR21##
 4. Themaltyl-2-methyl-pentenoate of claim 1 wherein R has the structure:##STR22##
 5. The maltyl-2-methyl-pentenoate of claim 1 wherein R has thestructure: ##STR23##